Color compositions containing salts of monoquinonyl-acid-amides



Patented Dec. 25, 1945 COLOR COMPOSITIONS CONTAINING SALTS OF MONOQUlNONYL-AClD-AMIDES Roy Herman Kienle and Chester Albert Amlek, Bound Brook, N. 3., asaignors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application July 1,1943,

Serial No. 493,130

i Claims. (01. 8-70) This invention relates to a new type of dyeing and printing assistant, dye compositions containing these assistants and products printed therefrom.

Use of printing-colorpaste containing dyes, particularly in printing operations using vat dyes, is sufllciently well-known so that the procedure has become almost standardized. The actual color source may be either a dye paste or a dye powder. In addition to the real color, a dye paste usually contains agents to prevent drying-out, settling and/or freezing. Dye powders, not being subject to these difllculties, do not require these agents but they usually contain agents or are so processed as to promote dispersibility.

In either case, the dye paste or dye powder must be admixed with suitable thickener, usually a gum dispersion, to form a printing-color paste which is suitable for application. In the case of vat dyes, it is also necessary to add a reducing agent and usually an alkali. Because the color yield from printing-color pastes often decreases rapidly as the paste ages after being made up, these printing-color pastes are usually prepared by the fabric finishers just before they are to be used.

The printing-color pastes, however compounded, are then applied to textile, paper'or other fabric materials for decorative or protective purposes. The printed pieces are dried, aged in a steam ager, treated with an oxidizing agent, rinsed and finally dried. Usually in processing textiles, the printed fabric also is soaped at or near the boil with about a 0.1% soap solution and again rinsed before the final drying operation.

In making up and applying printing-color pastes it has been found that a material suitable for use as a printing assistant is of advantage in obtaining maximum color yield. The exact way in which these materials act to produce an improved color yield in printing is not entirely understood. It is with these printing aids or assistants that the present invention is particularly concerned.

Although printing aids are desirable in the printing-color pastes, the exact point at which they are added may vary. Dye pastes may contain printing aids as one of their components and printing-color pastes made therefrom will obviously contain the printing assistant. Where a printing assistant is not present in the dye paste,

it may be added at the time of making up theprinting-color paste.

It is preferable, however, that the printing assistant be incorporated in the actual dye paste. Their addition, at the proper point in the manufacture of the paste is not only easier, but in addition they are thus generally more uniformly dispersed throughout a printing-color paste made therefrom. As a result, the printing assistants usually operate more effectively when the printing-color paste is finally applied to the fabric.

It is only relatively recently that dye powders suitable for use in making iip printing-color pastes have been available. Most of'the printing aids previously used in dye pastes, being either liquid in form or extremely hydroscopic, can not be used with dye powders, the latter being necessarily limited to the use of dry solids. Nevertheless, it is desirable that printing assistants be incorporated in the powders at the time of manufacture for the same reasons which apply in the case of dy pastes.

Dye pastes containing various liquid printing amines; silver salt (sodium anthraquinone betasulfonate); anthraquinone and certain metal salts such as those of cobalt and iron.

Unfortunately. most of these printing aids previously used are not as satisfactory as may bedesired. Many of them will not in all cases produce the intensification of color for which they were intended. Others, such as the polyhydric alcohols, cause deterioration of the printing-color pastes so that marked variations in the strength of prints therefrom are observable even after the printing-color paste has been allowed to stand for only a relatively short time. Many-of them are satisfactory with some colors but have an adverse effect on others, even to the extent of visibly altering the shade. None of them are suitable without modiflcation for use both in paste and powder compositions.

There remains, therefore, a demand for suitable printing assistants which will produce a satisfactory color intensification and will not cause deterioration of the dyeing or printing composition on standing. Preferably also, theassistants should be useful both with dye pastes and dye powders and in addition should be readily available or cheaply and easilyprepared. It is, therefore, the object of the present invention to provide a new type of printing assistant which possesses these desirable properties.

In general the objects of the present invention are accomplished by using as a printing assistant one or more of the salts of monoquinonylamides of dicarboxylic acids represented by the general formula i R: in which Ac represents the residue of a cyclic or aliphatic dicarboxylic acid, Q represents a quinonyl radical and R1, R2 and Rs represent hydrogen or an alkyl, aminoalkyl, alkylol or aryl radical. Typical of the salts of the present invention are the ammonium and ethanolamine salts of monoalpha-anthraquinonyl fumaramide which may be represented respectively by the formulae:

NH-C o-cn Ire-r o-Nn.

and

NH-C o-cn BIC-(ii 0-NHa-CHr-CHr-OH So far as the present invention is concerned the assistants may be added to the printing-color pastes in any of several ways during the compounding of the latter. They may be incorporated into the thickener; into the dye pastes or powders or may be blended directly into the printing-color paste. However, as pointed out above, it is preferable that they be incorporated in the dye p ste or powder during manufacture.

The use of this new class of printing assistants possesses a number of important advantages. These compounds are dry solids, which may be readily powdered and blended in dye powders but are also soluble or dispersible in dye paste suspensions. They have, therefore a general application in both dye pastes and dye powders. They do not cause deterioration of printing-color pastes on standing. They encourage the production of excellent color yields evenunder hot ageing conditions. Their use is simple since they may be employed as powders, as suspensions in water or alcohol.

The use of this new class of printing assistants a number of important advantages. These compounds are dry" solids, which may be readily powdered and blended in dye powders. In addition, they are either soluble or dispersible in dye-paste suspensions. They have, therefore, a general application since they may be incorporated into both dye pastes and dye POWdEH. They do not cause deterioration of printing-color pastes on standing. They encourage the production of excellent color yields even under hot ageing conditions. Their use is simple since they may be employed as either powders or as suspensions in water or alcohol, producing excellent color yields whatever the mode of admixture.

In preparing the salts to be used as printing assistants according to the present invention a monoquinonyl amide of a dibasic acid is usually reacted with ammonia or an amine. Many of the known amines react in this way to form suitable printing assistants. These include the primary alkyl and aryl amines, the secondary and tertiary alkyl amines and the alkanol amines. Therefore, without departing from the scope of the invention, the group in the generic formula may represent either the ammonium radical (-NHi) or a substituted ammonium group in which R1, R2 and R: may be quite widely varied.

Particularly good printing assistants are obtained from primary alkyl amines such as monoethyl amine, monopropyl amine and the like and the alkanol amines such as the methanol, ethanol and isopropanolamines and the like. However, similarly useful salts are also obtained from polyalkyl amines such as methylethyl amine, diethyl amine, di-n-butyl amine and the like and alkylene polyamines such as ethylene diamine and the like. Tertiary amines such as trimethyl amine also gave useful salts but are not ordinarily practicable. Arylamines such as aniline and naphthylamine and alkaryl amines such as the toluidines, xylidines and the like also yield similarly useful salts if properly reacted. R1, R1 and R: may therefore represent hydrogen, or an alkyl, aminoalkyl, alkylol, aryl or alkaryl radical, depending upon the particular amine used to form the salt to be used as a printing aid.

One factor however should be pointed out in connection with the preparation of the salts of the present invention. In reacting a material such as a mono-alpha-anthraquinonyl dicarboxylic acid amide with many amines either of two reactions may occur. At low temperatures, salts such as'those of the present invention are formed. 0n the other hand, at higher temperatures condensation occurs with the formation of a dicarboxylic acid diamide. These diamides are also similarly useful but are not intended to be within the scope of the present invention, being specifically set forth in our copending applications for United States Letters Patent, Serial Nos. 493,134, 493,135 and-493,136 flied of even date.

In preparing the salts to be used as the printing assistants of the present invention, the dicarboxylic acid from which they are derived may be quite varied. Suitable acids include both cyclic and/or aliphatic dicarboxylic acids. Of the cyclic dicarboxylic acids. phthalic-acid is perhaps the most common and its derivatives have been found to give good results when used according to the present process. The invention however is not meant to be so limited but includes derivatives of such acids as isophthalic, terephthalic, polyhydrophthalic, endoalkylenepolyhydrophthalic acids such as endomethy'lene-tetrahydrophthalic and endoethylene-hexahydrophthalic acids and the like, and the naphthalic acids as well as substituted acids derived therefrom.

Where derivatives of aliphatic dicarboxylic acids are used, the original acid or anhydride may be varied over a considerable range. It the original aliphatic acid is considered to have the seneric formula v coon coon

in the case of the anhydride; 1! may have substantially any value from zero, as in oxalic acid, to about eight. Accordingly, a: may be as in'the case of oxalic acid or a small even number not greater than 2y. Where 1! is greater than about six, difficulties are encountered in preparing the derivatives. Above about 11:8, there is a tendency for the compounds to be too insoluble for satisfactory use. The acids may be either saturated acids such as malonic, succinic, glutaric, adipic, azelic, sebacic, and the like or unsaturated acids such as maleic, fumaric and the like.

As pointed out in connection with the generic formula, Q represents a quinonyl group such as those of the naphthoquinones and anthraquinones. Paraquinonyl derivatives such as those from 1,4-naphthoquinone and LG-anthraquinone were found to give particularly good results. The

invention however is not necessaril so limited. Similarly good results were obtained, for example, from the derivatives of beta-naphthoquinone and beta-anthraquinone.

While the dye and printing paste compositions of the present invention are not limited to the use of any particular dyes or dye forms, they are especially suitable for use with vat-dyes in either paste or powder form. Particularly good results may be obtained using the vat-dye powders of high autodispersibility set forth in Crossley et al., United States Reissue Patent 21,402, reissued March 19, 1940. By combining the color materials of that patent into printing-paste compositions containing the printing assistants of the present invention, the full advantages of both may be gained with a resultant simplicity in use and excellence of shade and sharpness of color.

Printing pastes made in this way have the particular advantage that the dyes remain in a highly dispersed state as individual particles rather than as dispersions of particle aggregates. In the present specification and claims, where highly-dispersed dyes are referred to, reference to pastes in which the dye particles are so dispersed is intended.

The invention will be more fully set forth in connection with the following examples which are intended to be illustrative and not by way of limitation. All parts are by weight unless otherwise noted.

In the succeeding examples, test prints were made on 'tWo different types of fabrics. When rayon is referred to, a titanium-dioxide-pigmerited, all-viscose rayon flat crepe was used. The cotton fabric referred to is an 80 x 80 bleached, unmercerized, cotton print-cloth. Ageing of the prints was carried out in a steam ager which was constructed in such a manner that controlled temperatures could be used. The temperature range normally used was l00105 C. Those ageings referred to as plant or hot ageings were carried out in the temperature range of about 106-110 C. In the case of the cotton prints ageing periods of 3 minutes, 5 minutes or both were used. On rayon, ageing periods of 5 and 10 minutes or both were used. The shortest period which gives a satisfactory ageing is preferable.

Example 1 A paste was prepared by siurrying 2,000 parts of 1'77 British gum (Stein Hall) in 5,000 parts of water and the mixture wa heated with continuous stirring until the temperature reached about 185 C. Heating was continued for about 1% hours after 'which 450 parts of powdered sodium carbonate and 450 parts of powdered potassium carbonate were added and the mixture stirred until the carbonates dissolved. Heating was discontinued but stirring was continued until the temperature reached approximately 150 F. at which time 700 parts of sodium sulfoxylate formaldehyde were dissolved therein. Subsequently, 600 parts of glycerine were added and the paste bulked to about 10,000 parts. Stirring was continued until the paste cooled to room temperature. In the succeeding examples this paste is referred to as thickener A.

Example 2 2,100 parts of B-2 British gum, 200 parts of,

tapioca flour and 500 parts of cornstarch were added to 2,500 parts of water and heated over a steam bath for approximately 1 /2 hours after the temperature reached about 185 F. The source of heat was then removed but stirring was continued until the temperature decreased to 130 F. at which time 3,100 parts of potassium carbonate which has been previously dissolved in hot water was added to the cooked gum. 1,100 parts of sodium sulfoxylate formaldehyde were added to the common mixture at a temperature of about 150 40 F. Subsequently, 1,400 parts of glycerine were added and after thorough stirring the whole was bulked to about 10,000 parts. The mixture was cooled and stirred continuously until the mass reached room temperature. In the succeeding examples this mixture is referred to as thickener B.

Example 3 720 parts of 3-2 British gum and 720 parts of KAC-4 gum (Stein Hall) were added to 5,600 parts of water and heated over a steam bath for approximately 1% hours after the temperature reached 185-190 F. The source of heat was then removed but stirring was continued until the temperature decreased to 120 F. at which time 1,200 parts of potassium carbonate which had been previously dissolved in 1,000 parts of water was added to the cooked gum. 1,560 parts of sodium sulfoxylate formaldehyde were dissolved in 1,500 parts of water at a temperature of about 140 F. and added to the common mixture with stirring until the Whole was thoroughly mixed. 360 parts of glycerine were then added and after thorough stirring the whole was bulked to 12,000 parts. In the succeeding examples this mixture is referred to as thickener C.

Example 4 amount was entered into a ball mill, water added to reduce the dye content to approximately 15% and the mix was ground for 25 hours. This 15% Pink FF water paste will be hereinafter known as the blank."

Suflicient Vat Pink FF deflocculated presscake containing approximately 30 parts 'of pure dye was entered in a ball mill together with 6 parts of the ethanolamine salt of mono-alpha-anthraquinonyl phthalamide. A sufficient amount of v water was added to the mixture to reduce the dye content to approximately 15% and the mixture was then ground for approximately 24 hours. Thisproduct and the blank were then analyzed for extracted solids, pastes prepared with thickener A and comparative prints made on cotton cloth.v Use of the printing assistant not only gave much better color yields as determined by spectrophotometric analysis corrected for the amount of real dye used. In addition, it also gave excellent results using only a five minute ageing time.

Example 5 5 parts of Dark Blue BO powder (C. I.-1099) of the strength known as "double type was pasted with 5 parts of water. ,To this mixture 90 parts of thickener C were added and intimately mixed therewith. This was the control sample. A second 5 parts of Dark Blue BO powder were pasted with 5 parts of a 20% suspension of the printing assistant of Example 4. Both samples were mixed thoroughly and then blended with 90 parts of thickener C., stirring until uniform. Both pastes were printed on cotton and aged for 5 minutes in a steam ager. The printed pieces were then oxidized, rinsed, soaped and dried in the usual manner. Prints from the paste containing the assistant were noticeably stronger and brighter than the prints made from the paste containing water only.

Example 6 The procedure of Example 5 was repeated exactly except that Yellow GC (C. I.-1118) containing approximately 1 part of real dye was used in place of the Dark Blue BO. Prints made from the paste containing the assistant were definitely stronger and brighter than prints made from the paste containing water only, especially when they were aged under practical mill conditions.

Example 7 blended with 14 parts of water and 80 parts of thickener B. After thorough mixing the printing pastes were printed on rayon and finished in the usual manner. Prints made from the saltcontaining paste again were noticeably stronger in color yield than those made from the pastes containing water only.

Example 8 The procedure of Example '7 was repeated using the ethylene diamine salt of mono-alpha-anthraquinonylsuccinamide as a printing assistant. Again definitely improved color yields were produced by the printing assistant.

Example 9 from the pastes containing the beta-anthraquinonyl fumaramide salt were much stronger and brighter than the prints obtained from the paste containing water only.

Example 10 The procedure of Example 7 was followed except that ethanol amine salt of alpha-anthraquinonyl fumaramide was used. Again the prints from the pastes containing the alpha-anthraquinonyl monoamide of fumaric acid were also much stronger and brighter than the prints obtained from the paste containing water only.

Example 11 20 parts of ethanolamine salt of the alphaanthraquinonyl monamide of maleic acid were slurried with parts of water and ground into a ball until the suspension is uniform. Three parts of this suspension were mixed with 6 parts of Orange R powder (C. I.--1217) prepared according to U. S. Reissue Patent 21,402 and containing about 2.4 parts of real dye. After thorough mixing of the assistant and the color, 91 parts of thickener A was added and the mixture was stirred until it was homogeneous. A second 6 parts of Orange R powder was slurried with 3 parts of water and 91 parts of thickener A. Bimilar pastes were also prepared with thickener B. Each of these pastes were printed on rayon and on cotton, dried and aged. After ageing the pieces were oxidized, soaped, rinsed and dried. Prints obtained from the pastes containing the salt of the amide were in both cases stronger and brighter, both on rayon and cotton, than prints obtained from the paste containing water only.

4 Example 12 The procedure of Example 11 was repeated except that the aniline salt was used to replace the ethanolamine salt. In this case again the use of the printing assistant increased the color yields over that obtained from the pastes which contain water only.

Example 13 Example 12 was repeated using the alpha-naphthylamine salt. A substantially similar result was obtained, however the color was not quite as clear.

Example 14 Example 15 Again the procedure of Example 11 was .followed but using the ammonium salt. Again definitely better color yields were produced. It was also found that the requisite age ng time could be reduced over that required when the paste contained no assistant.

Example 16 The ethanol amine salt of beta-naphthoquinone was substituted for the printing assistant of Example 11. Again it was found that the presence of the salt produced prints that were both clearer and brighter than when it was omitted.

We claim:

1. A color composition comprising a vat dye and a salt of a monoqu nonyl amide of a dicarboxylic acid having the general formula:

where R is a member of the group consisting of the alkyl, aminoalkyl, alkylol and aryl radicals, Q represents a radical selected from the group consistingof the naphthaquinonyl and anthraquinonyl radicals, and Ac represents the residue of an acid selected from the group consisting of the cyclic and aliphatic dicarboxylic acids.

2. A dye powder composition comprising a vat dye and a dry, powdered salt of a monoquinonylamide of a dicarboxylic acid represented by the formula:

where R is a member of the group consisting of the alkyl, aminoalkyl, alkylol and aryl radicals, Q represents a radical selected from the group consisting of the naphthaquinonyl and anthraquinonyl radicals, and Ac represents the residue of an acid selected from the group consisting of the cyclic and aliphatic dicarboxylic acids.

3. A dye composition comprising a vat dye powder of high autodispersibility and a dry, powdered salt of a monoquinonyl amide of a dicarboxylic acid represented by the general formula:

where R is a member of the group consisting of the alkyl, aminoalkyl, alkylol and aryl radicals, Q represents a radical selected from the group consisting of the naphthaquinonyl and anthraquinonyl radicals, and Ac represents the residue of an acid selected from the group consisting of the cyclic and aliphatic dicarboxylic acids.

4. A color composition according to claim 1 in which R represents an alkyl radical.

5. A color composition according to claim 1 in which R represents an alkylol radical.

6. A color composition according to claim 1 in which R represents an aminoalkyl radical.

7. A printing paste composition comprising a dye; a thickener and a dry, powdered salt of a monoquinonyl amide of a dicarboxylic acid represented by the general formula:

where R is a member of the group consisting of the alkyl, aminoalkyl, alkylol and aryl radicals, Q represents a radical selected from the group consisting of the naphthaquinonyl and anthraquinonyl radicals, and Ac represents the residue of an acid selected from the group consisting of the cyclic and aliphatic dicarboxylic acids. 1

9. A method of printing with a vat color which comprises printing with a printing paste composition comprising a vat dye, a thickener and a dry, powdered salt of a monoquinonyl amide of a dicarboxylic acid represented by the general formula:

where R is a member of the group consisting of the alkyl, aminoalkyl, alkylol and aryl radicals, Q represents a radical selected from the group consisting of the naphthaquinonyl and anthraquinonyl radicals, and Ac represents the residue of an acid selected from the group consisting of the cyclic and aliphatic dicarboxylic acids.

10. An article of manufacture comprising a fabric printed with a composition comprising a vat dye, and a dry, powdered salt of a monoquinonyl amide of a dicarboxylic acid represented by the general formula:

I where R is a member of the group consisting of 

